Foreign



Patented Jan. 21, 1958 Unite tates 3'-positions either a hydroxyl groupor a substituent convertible into a hydroxyl group, such as a halogenatom 2820783 for example, chlorine, or an alkoxy group of lower mo-UPRIFE OUS DISAZQ.DYESTUFF5 lecular weight, advantageously a methoxygroup. Ac-

cordingly, there may be mentioned as diamines, for ex- Henrr Riat,Arlesheim, Switzerland, assrgnor to Ciba Lnnample, 3;3' dihydroxy4:4-diaminodiphenyl,3:3-dichloted, Ease! Switzerland a Swiss firmro-4:4--diaminodiphenyl, 3:3'-diethoxy-4:4 diaminodi- N0 DrawingApplication J n 7 1954 phenyl, and especially3:3'-dirnethoxy-4:4-diaminodi- Serial No. 435, 94 p y h 10 Thealkylamino group Y int e coupling components in Claims pnontyapphcauonSwitzerland June 1953 the Formula may be a dialkylamino group or more Cg, 250-143 especially a monoalkylamino group. There come intoconsideration alkylamino groups containing saturated or unsaturatedaliphatic hydrocarbon radicals and the latter This invention Provides116W cupfiferous disazodye- 15 may contain substituents, for example,cyano, hydroxyl stufis which, for example, like the dyestufi of theformula or alkoxy groups or aryl radicals. In general it is of Ho3s-SOSH H03 SOaH correspond to the general formula advantage to usecoupling components of the Formula 5 (2 Y ()Cu-O 0ouo 3|? in which Yrepresents an alkylamino group which is adwhich contain an alkylaminogroup of which the alkyl vantageously of low molecular weight and maycontain radical contains only a few, for example, 1-4 carbon furthersubstituents. atoms. Valuable results are obtained, for example, withThe invention also includes a process for making the coupling componentsof the aforesaid kind in which the aforesaid cupriferousdisazo-dyestufis, wherein a disazoalkylamino groups contain one or twohydroxyl groups dyestufl of the formula as substituents in the alkylradical. Such alkyl radicals SOaH 5 OH r r H0 38 S 0 311 HO 3S- in whichX represents a hydroxyl group or a substituent advantageously have theconstitution convertible into a hydroxyl group, and Y represents an Halkylamino group which is advantageously of low molecu- 5 lar weight andmay contain further substituents, is treated CH1 "(|7 H with an agentyielding copper in such manner that the \OH correspondingbis-(orthozortho' dihydroxyazo) copper complex is obtained, whennecessary, accompanied by the conversion of the substitueut X into ahydroxyl group.

The disazo-dyestufis of the Formula 3 used as starting materials in thepresent process can be made by coupling a tetrazotized diamine of theformula in which n represents the whole number 1 or 2.

As examples of suitable coupling components there may be mentioned thefollowing compounds: l-methylaminoor l-ethylamino-8-hydroxynaphthalene3:6-disulfonic acid, 1-dimethylamino-8-hydroxynaphthalene-3:6-disulfonic acid, 1-(fi-hydroxyethylamino)-8-hydroxy- (4) X Xnaphthalene-3:6 disulfonic acid, 1 isopropylaminoor 1 isobutylamino 8hydroxynaphthalene-3 :6-disulfon1c O acid, 1-(Bz'y-dihydroxypropylamino)8 hydroxynaph- I thalene-3z6-clisulfonic acid, l-(fior 'y-hydroxypropyD-amino-8-hydroxynaphthalene 3:6-disulfonic acid, l-n on both sides withcouphng components of the constitupropylamino 8 hydroxynaphthalene 3z6disulfonic acid tion l-allylamino-8-hydroxynaphthalene 3:6-disulfonicacid, l-(B-methoxyethylamino) 8 hydroxynaphthalene-3:6- (8) H0 Ydisulfonic acid and l-benzylamino-8-hydroxynaphthalene- 3:6-disulfonicacid.

The coupling components of the Formula 5 can be H03S 803E obtained bymethods in themselves known, for example,

by alkylating 1-amino-8-hydroxynaphthalene-3:6'd1sulionic acid.l-rnonoor 1-di-(hydroxyalkylamino-S-hy- X and Y in the Formulae 4 and 5having the meanings clroxynaphthalene-3:6-disulfonic acids can beobtained, given above. with advantage, for example, by reacting theamino-sul- As diamines of the Formula 4 there are used 4:4'-diionicacids With hydmiiyalkylhahdes, advantageously 111 aminodiphenylcompounds, which contain in the 3- and an aqueous medium and in thepresence of an acid-binda ing agent; Depending on the reactionconditions, the hoiceof the acid-binding agent and the quantity of thehydroxyalkyl halide l-monoor di-(hydroxyalkylamino)-8,-hydroxynaphthalene disulfonic acids can be obtained. Mixtures ofl-monoand di-(hydroxyalkylamino)-8-hydroxynaphthalene disulfonic acidscan also be obtained iri'thisrnanner, and these mixtures may also beused as coupling components for preparing the starting materialsalkaline medium, for example a medium rendered alkaline to the formulaHO-CHr-CHfiNH 0-Cu-0 SOaH with an alkali carbonate, and for couplingtetrazotized 3:3'-dihydroxy-4:4-diamin-odiphenyl a strongly alkalinemedium is indicated, for example, a medium rendered alkaline with analkali hydroxide or an alkaline earth metal hydroxide, and/or thesecouplings are advantageously assisted by suitable additions, such asalcohol or pyridine. I i '1 The treatment with the agent yielding coppermay also be carried out in known manner. In all cases it must be carriedout in such manner that the corresponding bis-(ortho:ortho'-dihydroxy-azo)-copper complex is obtained, and it is knownthat the reaction conditions must usually be more energetic when anortho-alkoxy-ortho'-hydroxyaz'o-grouping or an ortho-halogenorthoflhydroxy-azogrouping is present, than when anortho:ortho'-dihydroxy-az o-grouping is present. While it is generallysatisfactory 'to carryout the metallization in a weakly acid medium,'forexample, withcopper sulfate with the additi'on'of sodium ace tate,in the case of an ortho:ortho'-dihydroxy-azo-grouping, in other cases itis recommended to carry out the metallization with complex copper amminecompounds, for example, copper tetrammine compounds obtained withammonia, pyridine, an alkylamine or a hydroxyethylamine. The cupriterousdyestulis so obtained correspond to the above Formula 2. The latterformula as well as the Formula 1 undoubtedly represents thestoichiometric quantity of copper and the correct position of the copperatom in the complex, but the distribution of the main and secondaryvalences in the complex union of the copper to the dyestufi has notyetheen established with certainty. The new cupriferous dyestufis of theFormula 2 are suitable for dyeing and printing a very wide variety ofmaterials, especially cellulose-containing materials such as cotton,linen, and artificial silk or staple/fibers of regenerated cellulose.The .dyeings aredistin'guished by their good fastness' to light and ingeneral by. other good propertiesof fastness, forexample, a relativelygood fastness to acid and perspiration. The new dyestufifs are alsoespecially valuable because in general they yield extraordinarilygreenish blue ltints, which it was not possible to obtain with thedyestuffs ofsimilar type hitherto known. The tints of the dyeings arewell maintained in artificial light. Viscose artificial silk thatnormally yields streaky dyeings is uniformly dyed by the new dyestuffs.

The following examples illustrate the invention, the parts andpercentages being byweight:

Example 1 l 1 (5 hydroxyethyl) amino 8 hydroxynaphthalene-3:6-disulfonic acid. When the coupling is finished the solution isheated to 70 C., and the disazo-dyestuff is' precipitated by theaddition of sodium chloride and liltered ofi. It dissolves in water witha blue coloration and dyes cotton blue tints. Y

In order to convert the dyestuff into its copper complex, the dyestulfpaste is dissolved in 1500 parts of water and mixed with 50 parts ofmonoethanolamine. A-solution of 55 parts of crystalline copper sulfate,parts of ammonia solution of 25 percent strength and parts of water arethen added, and the whole is heated for 14 hours, while stirring andrefluxing, on a boiling water bath. The copper complex so formed whichcorresponds SOaH SOaH isthen salted out by the addition of sodiumchloride, filtered ,ofi and dried. The dyestufi, isa dark powder whichdissolves in .water with a greenish blue coloration and dyes, cottonclear greenish-blue tints;

The 1 (13 hydroxyethyl) amino 8 hydroxynaphthalene-3t6-disulfonic acidused in this example is obtained by reacting ethylene chlorhydrin orethylene oxide (about 1.5 mols) with 1-amino-8-hydroxynaphthalene-'3z6-disulfonicacid (1 mol) in aqueous solution and in Similardyestuffs, which likewise dye cotton greenblue tints, are obtained bythe procedure described above except that, instead of.1-(fi-hydroxyethyl)-amino-8-hydroxynaphthalene-3 6-disulfonic acid, thecorresponding quantity of one of the vfollowing coupling components isused:

(1) l ethylamino 8 hydroxynaphthalene 3:6 '-disulfonic acid, (2) 1isopropylamino 8 hydroxynaphthalene 3:6

disulfonic acid, (3) l isobutylamino 8 hydroxynaphthalene 3:6-

disulfonic acid, 7 (4) 1 allylamino 8 hydroxynaphthalene 3:6 Adisulfonicacid, 7 (5) 1 benz ylamino- 8 hydroxynaphthalene 3:6 disulfonic acid,(6) 1 (,3 hydroxypropyl) 7 amino 8 hydroxynaphthalene-3t6-disulfonicacid, (7) 1 ('y hydroxypropyl) amino 8hydroxynaphthalene-3c'6-disulfonic acid, a (8) l (5: dihydroxypropyl)amino 8 hydroxynaphthalene-3:'6-disulfonic acid, (9) 1 (B cyanoethyl)amino 8 hydroxynaphthalene-3:6-disulfonic acid, 7 (10) 1 (5methoxyethyl) amino 8 hydroxynaphthalene-3 6-disulfonic acid, l1) 1methylamino 8 hydroxynaphthalene 3:6 -disulfonic acid.

These coupling components can all be made, in a manner. analogous tol-(B-hydroxyethyl)-amino-8-hydroxynaphthalene-3:6-disulfonic acid, from1-amino-8-hydroxynaphthalene-3:6-disulfonic acid and the correspondingalkyl halide or hydroxy-alkyl halide or acrylonitrile (No. 9)..

Example 2 21.6 parts of 3:3-dihydroxy-4:4'-diaminodiphenyl aretetrazotized. Thetetrazo-compound is neutralized with sodium carbonateand filtered OE, and then introduced into a mixture of 84 partsof1-benzylamino-S-hydroxynaph: thalene-3z6-disulfonic acid, 100 parts ofwater, 100 parts of an aqueous suspension of calcium hydroxide of.25percent strength and 50 parts, of pyridine or picoline. The

aea fles whole is stirred for 12 hours at 10-15 C. The disazocotton isthen rinsed and finished in the' usualmanner. dyestufi formed isisolated by acidification and separation There is'obtained apuregreenish blue dyeing which is by filtration, and it is convertedinto its copper complex fast to light.

by heating it for one hour at 70 C. with an ammoniacal The formulae ofsome of the claims contain twice the solution of copper sulfate(corresponding to 50 parts of symbol Y. It is to be understood thatthese claims CuS0 .5H 0). The copper complex 1S Worked up in theencompass not only symmetrical, but also asymmetrical usual mann r andf' It IS a blaqklsh P Whlch dyestuffs wherein the Ys are different fromone another dissolves 1n water with a blue coloration and dyes cottonalthough each Y Should be consistent with the definition greenish bluetlmsgiven in the particular claim.

Example 3 What is claimed is: 24.4 parts of3:3'-dimethoxy-4:4'-diaminodiphenyl are 1. A cupriferous disazo-dyestuffof the formula Y 0--0u0 0-0u-0 Y H038 SOEH HOaS eOtH tetrazotized, andthe tetrazo compound is coupled in a in whichYrepresents an alkylaminogroup. solution, rendered alkaline with sodium carbonate, of 35 2. Acupriferous disazo-dyestufi of the formula Y OCu O OCl10 parts of1-ethylamino-8-hydroxynaphthalene-3:6-disulin which Y represents anamino group substituted by a fonic acid. To the so-obtaineddiazo-monoazo commember selected from the group consisting of a benzylpound a solution, rendered alkaline with sodium carradical, an aliphatichydrocarbon radical containing at bonate, of 36.3 parts ofl-(fl-oxyethyl)-amino-8-hydroxythe most four carbon atoms, ahydroxyalkyl radical connaphthalene-3:6-disulfonic acid is added. Whenthe coutaining at the most two hydroxyl groups and at least two pling isfinished the disazo dyestuff is isolated in known but at the most threecarbon atoms, an alkoxyalkyl group manner and converted into its coppercomplex according containing at the most four carbon atoms, and a cyanmto the method described in Example 1. The copper comalkyl radicalcontaining at the most four carbon atoms. plex dyes cotton pure greenishblue tints. 3. A cupriferous disazo-dyestufi of the formula H0; 80311HO: SOaH Example 4 in which m represents a whole number of at the most4. 100 parts of cotton are entered at C. into a dye- A cupriferousdisazo'dyestufi of the formula Z-NH (|)-Cu 0 OCu0 HN-Z Hmsson; I Hms-SOsH bath which contains in 3000 parts of water 0.5 part of the in whichZ represents a hydroxyalkyl radical containing cuprlferous dyestuftobtained as described in the first and at the most two hydroxyl groupsand at least two but at second paragraphs of Example 1. Dyeing iscarried on for the most three carbon atoms. /6 hour while raising thetemperature to C., 30 parts 5. A cupriferous disazo-dyestufl of theformula i i H-(--(';- HgCNH OCu-O 0-cu HNCH2-(-C'!)H N=N N=N uossmsomBoss $013 of crystalline sodium sulfate are added, and then dyeing inwhich n represents a whole number of at the most 2. is continued for afurther V2 hour at 90-95 C. The 6. The cupriferous disazo-dyestuff ofthe formula HO-CHa-CHa-NH 0-Gu0 0Cu0 HN-CHg-CHa-OH HO: SOaH B018 801Boss- -8. The cupriferous disazo-dyestuff of the formula QHqC-NH OGuO-Cu HI -OHPO N=N N=N HOaS- SOaH H0; 803B 9. The cupriferousdisazo-dyestufi'of the formula HO OH HaOHHgC-NH 0Cu 0- u-0 HNVCH('JHCH;

I N=N- N= Ems SOaH 'noss- 803B 10. The cupzife'rous disazo-dyes'tufi' ofthe' formula SVOaH SOaH References Cited in the file of this patentUNITED STATES PATENTS Straub 'et a1. July 15, 1947 Straub et a1. Sept.9, 1947 267,049 Switzerland July 1, 1950 UNITED STATES PATENT OFFICECertificate of Correction Patent N 0. 2,820,783 January 21, 1958 HenriRiat It is hereb certified that error appears in the printedspecification of the above num ered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Columns 3 and 4, lines 15 to 22, right-hand portion of the formulashould appear as shown below instead of as in the patentcolumns 5 and 6,claim 3, the right-hand portion of the formula should appear as shownbelow instead of as in the patent- O ENC-Han SOaH same columns 5 and 6,claim 5, the upper left-hand portion of the formula should appear asshown below instead of as in the patent Signed and sealed this 10th dayof June 1958.

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Commz'esz'oher of Patents,

1. A CUPRIFEROUS DISAZO-DYESTUFF OF THE FORMULA